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1.
The reductions of Co(terpy)23+ and Co(edta)? complexes by ascorbic acid have been subjected to a detailed kinetic study in the range of pH =1–10.9. For each complex the rate law of the reaction is interpreted as a rate determining reaction between Co(III) complex and the ascorbic acid in the form of HA? (k1) and A2? (k2), depending on the pH of the solution, followed by a rapid scavenge of the ascorbic acid radicals by Co(III) complex. With given Ka1 and Ka2, the rate constants are k1 = 0.25 and 9.87 × 10?5 M?1s?1, k2 = 1.28 × 106 and 18.7 M?1s?1 for Co(terpy)23+and Co(edta)? complexes, respectively, at T = 25 °C and μ = 0.50M (terpy)and 1.0 M (edta) HClO4/LiClO4. The mechanism of the reaction is discussed on the basis of Marcus theory for outer sphere electron transfer process. Spin change and charge effect, duly considered, account for the non‐adiabatic behavior in the reduction of Co(edta)? complex. 相似文献
2.
Stepanenko O. N. Potaskalov V. A. Trachevskii V. V. 《Russian Journal of Coordination Chemistry》2001,27(1):51-56
Heteroligand cobalt(III) chelates with triethanolamine and glycine, [Co(HTetm)GlyH2O] · 2H2O (I) and [Co(HTetm)GlyNH3] · 2H2O (II) (H3Tetm is N(C2H4OH)3 and HGly is glycine), were synthesized. The acidity constants of complex I were determined at an ionic strength of 0.1. The reactions of I with alcoholic solutions of acids, ammonia, and ammonium nitrate were studied. Binuclear complexes were obtained upon the interaction of I and II with CoCl2 · 6H2O. The complexes were characterized using UV–VIS (in aqueous and alcoholic solutions) and IR (in the solid state) spectroscopy. The 13C NMR spectra of solutions of Iand II were recorded. The plausible structures of the complexes are discussed. 相似文献
3.
The crystal structures of molybdocene‐amino acid compounds of the type [Cp2MoIV(κN, κO‐AA)]+Cl—·xH2O with AA = D ‐phenylalaninato (x = 1.5), DL ‐leucinato (x = 2) and DL ‐valinato (x = 1) have been determined (Cp = η5‐C5H5). The compounds feature an almost planar, five‐membered chelate ring of the aminocarboxylate moiety (deprotonated amino acid) with the molybdenum atom. In the phenylalaninato complex π‐stacking between the phenyl rings is found. The complexes were proven kinetically stable at pH < 1 for at least 24 h. 相似文献
4.
Kamal A. R. Salib Samy M. Abu El-Wafa Salah B. El-Maraghy Saied M. El-Sayed 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):131-138
Abstract Monosulfito and bis(hydrogensulfito) cobalt(III) complexes were prepared using sodium sulfite and sodium metabisulfite salts respectively. The two types of products showed different and characterizing patterns of IR and UV-visible spectra. They both contain Co-SO3 linkages and the sulfite groups have similar or different site symmetries in the same compound. 相似文献
5.
《液相色谱法及相关技术杂志》2012,35(15):3481-3488
Abstract A fast and convenient procedure is described for the HPLC separation of LSD and LAMPA. These compounds are separated by a reversed phase (C18) procedure using a binary solvent system of methanol and pH 3 phosphate buffer. Under these conditions all compounds are eluted in a retention volume of 27 mL or less. This procedure allows a forensic sample to be identified as LSD and to eliminate LAMPA as a possibility. 相似文献
6.
向日葵仁中绿原酸和咖啡酸的反相高效液相色谱法测定 总被引:9,自引:1,他引:9
建立了同时测定向日葵仁中绿原酸和咖啡酸的反相高效液相色谱法 ;采用美国Alltech公司的ALLTIMAC18 柱(250mm×4.6mmID,5μm) ,流动相为乙腈 -2 %(φ)乙酸溶液 (体积比15∶85) ,流速为1.0mL/min ,紫外检测波长327nm ;向日葵仁中绿原酸(chlorogenicacid)和咖啡酸(caffeicacid)在18min内得到很好的分离 ,该法简便、快速、结果准确、重复性好。 相似文献
7.
The metallosupramolecular chemistry of two enantiopure dicarboxylate ligands has been explored for their potential to form discrete or polymeric interlocked motifs. Consequently, both discrete and polymeric supramolecular complexes have been synthesised, yielding M2L2 metallomacrocycles ( 1 and 2 ), a heteroleptic M2L3 metallomacrobicycle ( 3 ), a non‐interpenetrated coordination polymer ( 4 ), and highly unusual chiral M8L8 squares ( 5 and 6 ). There appears to be a preference for the ligands to form M2L2‐type metallomacrocyclic structural units (which feature in 1 – 4 ), although these do not engage in any mechanical interlocking, which is perhaps a combined function of the ligand flexibility and relatively small pi‐surface contrasted to previous analogues. Using copper paddlewheel SBUs, chiral double‐walled squares ( 5 and 6 ) are formed with large internal cavities yet poor stabilities, unexpectedly featuring the paddlewheel motifs at the vertices of the polygonal complex. 相似文献
8.
The β‐pyranose isomer of D ‐galactosylamine ( 1 ) formed complexes with three different cobalt(III) fragments. Crystals containing the dication [Co(tren)(β‐D ‐Galp1N2H–1‐κ2N1,O2)]2+ ( 3 ) showed coordination through the anomeric amino group (N1) and the deprotonated hydroxy group (O2) of the 4C1 β‐pyranose form, which is also the major isomer of free galactosylamine. The cationic complexes [Co(fac‐dien)(β‐D ‐Galp1N2H–1‐κ2N1,O2)]2+ ( 4 ) and [Co(phen)2(β‐D ‐Galp1N2H–1‐κ2N1,O2)]2+ ( 5 ) were analysed by NMR spectroscopy and showed the same coordination mode as 3 . In terms of available ligand isomers it was shown that 1 exhibits an anomeric equilibrium in solution of both pyranose and both furanose forms as is typical for the parent glycose, galactose. 相似文献
9.
反相高效液相色谱法测定牙膏中的甘草次酸 总被引:1,自引:1,他引:0
采用反相高效液相色谱法测定了牙膏中的甘草次酸。在YWG C18(40mmi.d.×250mm,10μm)色谱柱上,以V(甲醇)∶V(001mol/LKH2PO4)=85∶15(pH30)的溶液为流动相,流速为10mL/min,紫外检测波长为254nm,室温下检测。甘草次酸用甲醇提取。甘草次酸的平均回收率为9961%~10167%,样品测试相对标准偏差为185%~316%。方法操作简便、快速和准确。 相似文献
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本文研究了2-(2-噻唑偶氮)-对-甲酚(TAC)与镍(Ⅱ)、钴(Ⅱ)螯合物的柱前衍生条件和液相色谱的分离条件。于KYWG-C_(18)柱上,用含有0.03mol/L KH_2PO_4-Na_2HPO_4(pH7.77)和2.5×10~(-4)mol/L TAC的甲醇-四氢呋喃-水(40∶10∶50 V/V)混合液为流动相,流速为1.0mL/min。于580nm处检测。该法用于四种标准合金中镍和钴的测定,回收率在98%~101.5%之间。Ni(Ⅱ)和Co(Ⅱ)的检出限(信噪比为2∶1)分别为0.2ng和1.5ng。建立了同时测定镍,钴的高灵敏、高选择性,快速的HPLC-光度法。 相似文献
14.
Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)‐Catalyzed Intermolecular Carboamination of Alkenes 下载免费PDF全文
Andreas Lerchen Tobias Knecht Dr. Constantin G. Daniliuc Prof. Dr. Frank Glorius 《Angewandte Chemie (International ed. in English)》2016,55(48):15166-15170
Herein, we report an unprecedented regioselective and entirely atom‐economic cobalt(III)‐catalyzed method for the non‐annulative, intermolecular carboamination of alkenes. The methodology enables the direct synthesis of unnatural amino acid derivatives and proceeds under redox‐neutral conditions with a completely regioselective C?C bond and C?N bond formation. Furthermore, this reaction exemplifies the inherently different mechanistic behavior of the Cp*CoIII catalyst and its Cp*RhIII counterpart, especially towards β‐H‐elimination. 相似文献
15.
《Journal of Coordination Chemistry》2012,65(18):1581-1586
Reaction of cis-diazidobis(ethylenediamine)cobalt(III)nitrate with ammonium thiocyanate in a 1?:?2 molar ratio in aqueous medium gave the title cobalt(III) compound, cis-[Co(en)2(N3)2]SCN, as reddish brown crystals in almost quantitative yield. The complex salt was characterized by elemental analysis, IR, electronic, 1H and 13C NMR spectroscopic studies. An X-ray structure determination revealed an ionic structure with the monoclinic space group P21/c, having cell dimensions a = 12.1950(6), b = 9.0317(5), c = 12.6017(7)?Å; β = 113.419(1)°, V = 1273.63(12)?Å3 and Z = 4. The structure was refined by a full-matrix least-square procedures to R 1 = 0.0297 and wR 2 = 0.0697. 相似文献
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17.
Andrew Zanella Robert Pinnell Jacob Gilbert Anthony Fucaloro 《Journal of solution chemistry》2008,37(12):1775-1783
Partial molar volumes (V
2°) have been determined at infinite dilution in aqueous solution at 20 °C for a series of octahedral N6-coordinated cobalt(III) species having five-coordinated ammonia ligands along with an N-coordinated linear alkyl amine whose
alkyl chain was varied from ethylamine to octylamine. The experimental values for V
2° are consistent with the relative sizes of the ligands but show increasing deviations from those predicted by computer modeling,
as the size of the cation increases, presumably due to the void space of the cation that increases with the size of the amine
ligand. The value of the partial molar volume at infinite dilution increased by about 16 mL⋅mol−1 with each added methylene group. 相似文献
18.
Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine
New complexes of the formulae K3[RhL
3]·2 H2O, [PdL]·H2O and [M(LH2)Cl2] [whereM = Pd, Pt andLH2 = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and1H-NMR spectroscopy.
Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)
Zusammenfassung Neue Komplexe der allgemeinen Formeln K3[RhL 3]·2H2O, [PdL]·H2O und [M(LH2)Cl2] mitM = Pd, Pt undLH2 = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und1H-NMR-Spektroskopie charakterisiert.相似文献
19.
Laura E. N. Allan Jarret P. MacDonald Amy M. Reckling Christopher M. Kozak Michael P. Shaver 《Macromolecular rapid communications》2012,33(5):414-418
Tetradentate amine–bis(phenolate) iron(III) halide complexes containing chloro substituents on the aromatic ring are extremely efficient catalysts for controlled radical polymerization. Molecular weights are in good agreement with theoretical values and polydispersity indexes (PDIs) are as low as 1.11 for styrene and methyl methacrylate polymerizations. Complexes containing alkyl substituents on the aromatic ring are less efficient. Kinetic data reveal activity for styrene polymerization among the fastest reported to date and initial studies implicate a multimechanism system. Despite the highly colored polymerization media, simple work‐up procedures yield pure white polymers. 相似文献
20.
K. Santhakumar N. Kumaraguru S. Arunachalam M. N. Arumugham 《Transition Metal Chemistry》2006,31(1):62-70
The kinetics and mechanism of reduction of the surfactant complex ions, cis-chloro/bromo(dodecylamine)(triethylenetetramine)cobalt(III) by iron(II) in aqueous solution were studied at 303, 308 and
313 K by spectrophotometry under pseudo-first-order conditions using an excess of the reductant. The second-order rate constant
increases with cobalt(III) concentration and the presence of aggregation of the complex itself alters the reaction rate. The
reductions are acid-independent in the range [H+] = 0.05–0.25 mol dm−3. Variation of ionic strength (μ) influences the reaction rate. Activation and thermodynamic parameters have been computed. It is suggested that the reaction
of Fe2+(aq) with the cobalt(III) complex proceeds by an inner-sphere mechanism. The critical micelle concentration (CMC) values of
these surfactant metal complexes in aqueous solution were obtained from conductance measurements. Specific conductivity data
(at 303, 308 and 313 K) served for the evaluation of the temperature-dependent CMC and the standard Gibbs energy of micellization
(ΔGm0). 相似文献